Search results for "cyclopropanation"
showing 10 items of 23 documents
Efficient microwave-assisted synthesis of PCBM methanofullerenes (C60 and C70)
2015
PCBM is a fullerene derivative (phenyl-C61-butyric acid methyl ester) considered to be one of the best n-type organic semiconductors and plays a relevant role in organic photovoltaic solar cells. Much effort has been devoted to the optimization of the synthesis of PCBM derivatives. In this paper, PC61BM and PC71BM fullerene mono-adducts but also PCBM-like derivatives are successfully prepared by a one- step cyclopropanation reaction under microwave irradiation. The products are collected in good yields in short time, during which isomerization of the open [5,6] to the closed [6,6] form takes place in situ. In addition, with the use of two cycles of irradiation, a series of mixtures of bis-a…
Homogeneous and supported copper complexes of cyclic and open-chain polynitrogenated ligands as catalysts of cyclopropanation reactions
1999
CuI and CuII complexes of cyclic and open-chain polyaza compounds have been tested as catalysts in the benchmark cyclopropanation reaction of styrene with ethyl diazoacetate. In general, only small amounts of copper are needed to promote the reaction. The catalytic activity depends on the structure of the ligand, e.g. amine–amides are more efficient than polyamines, and on the oxidation state of copper, CuII being more active than CuI. Given that CuI is the active species, these changes of behavior must be related to the stabilities of the complexes. The nature of the counterion also has a noticeable influence on the catalytic activity, the role of which is discussed. XAS measurements sugge…
ortho-Metalated Dirhodium(II) Catalysts Immobilized on a Polymeric Cross-Linked Support by Copolymerization. Study of their Catalytic Activity in the…
2008
Chiral ortho-metalated dirhodium(II) compounds containing the phosphine P(p-CH2═CHC6H4)3 have been efficiently immobilized by radical copolymerization with styrene and 1,4-divinylbenzene. Their cat...
First Diastereoselective Synthesis of (−)-Methyl Thyrsiflorin A, (−)-Methyl Thyrsiflorin B Acetate, and (−)-Thyrsiflorin C
2000
An efficient procedure for the synthesis of scopadulan diterpenes, using (+)-podocarp-8(14)-en-13-one 13 as starting material, is reported. This procedure has been used for the diastereoselective synthesis of (-)-methyl thyrsiflorin A (8), (-)-methyl thyrsiflorin B acetate (9), and (-)-thyrsiflorin C (7). Key steps in our strategy are the intramolecular cyclopropanation of diazoketone 19 and the regioselective cleavage of the cyclopropane ring.
Ligand Effects on the Chemoselectivity of Ortho-Metalated Rhodium(II) Catalyzed α-Diazo Ketone Transformations
1997
Rh2(OOCR)2(PC)2 complexes (PC = orthometalated phosphines, OOCR = carboxylates) with very polarizable ligands, such as aromatic rings directly joined to the rhodium atoms, control chemoselectivity in competitive metal carbene transformations of α-diazo ketones. These catalysts have a mixed set of ligands that allows choosing among a big selection of ligands to gradually affect the electronic and steric properties of the catalyst. Their selectivity depends on the electrophilicity of the ligands and the polarizability of the metalated aromatic rings. Thus, Rh2(OOCR)2(PC)2 compounds [PC = (C6H4)P(CH3)(C6H5), (p-CH3C6H3)P(p-CH3C6H4)2, (C6H4)P(C6H5)2; R = C3F7 or CF3] exhibit an exceptional sele…
Immobilized Chiral ortho-Metalated Dirhodium(II) Compounds as Catalysts in the Asymmetric Cyclopropanation of Styrene with Ethyl Diazoacetate
2007
Immobilization of ortho-metalated dirhodium(II) compounds has been achieved by a carboxylate interchange reaction between (M)-Rh2(l-protos)2[(p-XC6H3)P(p-XC6H4)2]2 diastereoisomers and carboxyethylpolystyrene polymer (PS-C6H4(CH2)2CO2H). The immobilized chiral catalysts have been tested in the standard reaction of asymmetric cyclopropanation of styrene with ethyl diazoacetate, giving higher yields than homogeneous chiral trifluoroacetate derivatives, but their diastereo- and enantioselectivities were lower. Some of the immobilized catalysts have proved to be very robust. The catalytic behavior of (M)-Rh2(O2C(CH2)2C6H5)2[(p-XC6H3)P(p-XC6H5)2]2 compounds has been studied as a model for the im…
High Enantiocontrol in the Intramolecular Cyclopropanation of Diazo Ketones Catalyzed by Dirhodium(II) Complexes with Ortho-Metalated Aryl Phosphine …
2001
[reaction: see text]. Chiral dirhodium(II) complexes, Rh2(O2CCF3)2(PC)2, [PCH = (p-CH3C6H4)3P, (m-CH3C6H4)3P], provide an excellent yield and a high enantiocontrol in the cyclopropanation of alpha-diazo ketones with gamma and delta double bonds. The ee values are significantly dependent on the solvent used; the best results are obtained using pentane.
Stereoselective synthesis of polyoxygenated atisane-type diterpenoids
2001
Abstract A new stereoselective approach to polyoxygenated atisane-type diterpenes starting from (S)-(+)-carvone is described. The key steps involve an intramolecular Diels–Alder reaction, an unusual intramolecular diazo ketone cyclopropanation of an unsaturated ketone, and a regioselective endocyclic cleavage of a cyclopropyl carbinyl radical as key synthetic steps. The synthesis of the bioactive polyoxygenated atisanes atis-16(17)-en-3,14-dione ( 2 ) and 3R-hydroxy-atis-16(17)-en-2,14-dione ( 3 ) following this approach is presented.
A unified synthetic approach to trachylobane-, beyerane-, atisane- and kaurane-type diterpenes
2006
A general synthetic approach to the polycyclic carbon skeleton of biogenetically related trachylobane, beyerane, atisane, and kaurane diterpenes from carvone is described. The skeleton of these diterpenes is prepared from a common intermediate, that is, 25, readily prepared from carvone using an IMDA reaction and an intramolecular diazo ketone cyclopropanation of an unsaturated ketone as key steps. The tetracyclic diterpene ring systems are obtained from this key trachylobane-type intermediate through the regioselective reductive cleavage of the cyclopropane ring, after adequate modification of the functionalization around the tricyclo[3.2.1.02,7]octane moiety.
Part II. Chiral dirhodium (II) catalysts with ortho-metalated arylphosphane ligands in the enantioselective intramolecular cyclopropanation of a race…
2006
Abstract In this report, chiral dirhodium (II) with ortho -metalated phosphane ligands, namely ( M )-Rh 2 (O 2 CR) 2 (PC) 2 [PC = ortho -metalated aryl phosphane, O 2 CR = carboxylate bridging ligands) ( 1a–g ), have been used for the intramolecular cyclopropanation of racemic1-diazo-6-methyl-3-(2-propenyl)-5-hepten-2-one ( 2 ), containing both a tri- and monosubstituted carbon–carbon double bond, in pentane. The highest level of regiocontrol has been obtained with chiral catalyst Rh 2 (O 2 CCH 3 ) 2 [( p -MeC 6 H 3 )P( p -MeC 6 H 4 ) 2 ] 2 ( M )- 1c , affording favorably trisubstituted cyclopropane 3 versus monosubstituted cyclopropane 4 in 74:26 ratio. An exceptional diastereoselectivity…